Radical addition reactions of halogenated olefins and compounds produced thereby



United States Patent "ice RADICAL ADDITION REACTIONS 0F I-IAEO- GENAT-EDOLEFINS AND COMPOUNDS PRODUCED THEREBY William T. Miller, Ithaca, N.Y.,assignor, by mesne assignments, to Minnesota Minin and ManufacturingCompany, St; Paul, Minn;, a corporation of Delaware No Drawing.Applicationiiily 12,1955 Serial No. 521,640

13 Claims; (Cl. 260-653) This invention relates to novel radicaladdition reactions of perhalogenated alkanes with halogenatedethylenically unsaturated compounds.

The principal reactions occuring in the process of the present inventionare as follows, in Which-OX is a perhalogenated alkane, i.e., aperhalogenatedmethane:

Iv FREE RADICAL ADDITION OF OX4 TO AN OLEFIN 0:0

acetyl, benzoyl and pelargonyl p'eroxides or other sources of freeradicals such as the compound:

If the radicalsforme'd by the dissociation of the methane do not attackthe olefinthe observed reaction products are decompositionproductsderived from the methane, and the'proeess of the presentinvention does not occur.

The initiation step is followed by a propagation step which can involvea nuniber of olefin molecules for every initiation. Aninitiatingsradical canreactwith an olefin 2,880,248 Patented Mar. 31,1959 molecule to form a" new larger radical, a process leading topolymerization, or stabilize itself by abstracting an atom from a nearbymolecule, a chain transfer reaction, with the formation of a new radicalwhich can continue the chain process and lead to a saturated product. Ifpolymerization predominates", relatively high molecular Weight productsare formed. When chain transfer is more important, the product isprimarily the monomer addi* tion product, and if both of these steps areslow, the intermediate radicals have a relatively long life' and coupledor disproportionation products are formed in significant quantities.

The radical formed-in the reaction of bromotrichloro methane with2-chloropentafluoropropeneis very unreactive. Polymerization does notoccur, but the chain'tra'lisfer step to form the monomer additionproductis also slow as indicated by the vigorous conditions required to efiectreaction. The intermediate radical has a relatively long life, and theprimary by-product ofthis reaction? is the coupled product C5C17F5(presumably CF C( CCl CICF CCI The reactivity of chlorofluoro freeradicals is indicated to be C F; C F:

ROFz- ROClF- RCF- ROC1- This is also the order which would be predictedon the basis of a steric effect.

An attacking radical, Equation 2, above, might attack either or bothends o'f'an unsymmetrical olefin withthe eventual formation ofeither-orboth-of the possible addi tion products. It hasbeen shown, however, thata cleancut orientation effect is operative in-free radical reactionsinvolving hydrogen-containing olefins, with only one of the two possibleisomers being formed. Furthermore; in every case the initial attack wason the most exposed p'osi tion to yield the intermediate radicalwhichwas predicted to be the most stable.

In the present invention the following illustrative products wereobtained from unsymmetrical perhaloolefinsz These products indicatethatthe initial attack by OX radicals is in each case on the exposed CFcarbon; These orientations are the ones which would :bepredicte'd fromsteric considerations.

The alkanes which may be added to halogenated olefins in accordance withthe present invention are those having the formula in which Y isfluorine or' chlorine and R1, is a pet-haloa'lkyl radical having notmore than 8 carbon atoms; and in which all of the halogen atoms arefluorine and/or 3 chlorine. The R radical may also contain a second un-I EXAMPLE 1 conjugated double bond.

Exemplary of the olefins contemplated are CF =CFCF Reaction ofhexafluompmpene with CBrCla CF2=CFCFZCF3, CFZ=CF(CF2)3CF3, d CF =CFCClCF and CF =CFCFClCF CFClCF d The most satisfactory olefins for radicaladdition reactions are the most reactive types, as evidenced by theirpolymenzability, provided effective chain transfer agentsHexafluoropropene, 21.5 grams (0.14 mole) was sealed in a glass ampoulewith 75 grams (0.38 mole) of CBrCl and placed in the S-bulb illuminator.The temperature was gradually raised from 60 to 100 C. over athirteenday period. The contents of the ampoule were distilled to areutilized for addition. However, useful syntheses are i ld; also obtainedwith less reactive olefins which have not 10 Grams been satisfactorilypolymerized alone and for which, al- (1) s lid carbon dioxide trap 3though the reaction occurs more slowly, the simultaneous (2) By, 68 to74 C 5.3 formation of polymer is not a problem. On the other (3) RP, 74to 102 C 4.4 hand satisfactory addition reactions are not obtained withy (4) By, 102 t 106 C. 28 disubstituted olefins of the general type, RCF=CFR (5) B1 106 to 145 C 12.5 in which R is a perhalogenated group.(6) B P 145 t 151 C 26.6 A number of transformations were performedstarting (7) R idu 10 with the monomer addition compounds in order toestablish structures and to extend the usefulness of the syntheticprocedures developed.

The addition product of bromotrichloromethane and 2-chloropentafluoropropene was converted to the following 1 CiBrclaFa,percent.

Fraction 1 was probably unreacted CF CF==CF Fraction 2 was probablymostly CF CBrFCBrF which boils at 72.5 C./760 mm.

compounds: Fraction 4 was mostly recovered CBrCl M11 01, CFaCBrClCFzCChGFaCCl=CFOCh OFIC ClzCClFCCh Acetone lZn HgO [HF CFICHCICFrCCl:CF;CC1=CFCC1|F CFaCChCClFCClF: CFsCC1=OFCGl1h CFsCCllCFaCChCFiCChCClFCF: CFaCCl=CFCF8 One of the unexpected and useful reactionsobserved Fraction 6 was redistilled and 6 grams of a centercut with thesodium iodide reagent is the splitting out of BrF were collected. Theproperties of this fraction were: B.P. from CF CBrClCF CCl in high yieldto form 149.9-150.2 C./ 740 mm.; d 1.9845; n 1.4063; RP.

78 to -84 C. MR for C BrCl F found, 43.2; cal- CF3CC1=CFCC13 culated43.30. It was tentatively assigned the structure it is observed that CBrCl F when treated With zinc CF CBrFCF CCl on the basis of its reactionwith sodium in dioxane or zinc in ether, is reduced instead of deiodidein acetone in a sealed tube at 100 C. for one and halogenated. Thereplacement of bromine by hydroone-third hours to form free iodine and aprecipitate of gen as a result of treatment with zinc and alcohol repre-NaBr and NaF and by analogy with other addition resents a useful newsynthetic method. actions studied. The olefin was not isolated.

The radical addition reactions of the invention may be Fraction 7 wascooled in ice and a solid material filtered effected using a molar ratioof perhalogenated alkane to off. After recrystallization from methanol,this solid halogenated monoolefin in the range of 1 to 1 to 20 to 1, amelted at 184 to 185 C. (sealed tube). It was thus temperature in therange of 20 C. to 250 C., preferably shown to be C Cl 25 C. to 150 C.,and reaction time of 30 seconds to 120 hours, preferably 5 minutes to 12hours. When a peroxide catalyst is used, it may be employed in aconcentration of 0.5 to 10 moles per 100 moles of olefin. The pressuremay be in the range of 1 to 100 atmospheres, preferably 1 to 25atmospheres; autogenous pressure is generally used.

EXAMPLE 2 Reaction of 2-ch loropentafluoropropene with CBrCl Thefollowing reactions were carried out to prove the structure of theaddition product of CBrCl and CF CF2 H O OFaCCl=GFCFs "H CFaCCl=CFCCh C-acchcFzCClx lKMnOt cFtcoln 001,001

The products produced by the process of the invention It was found thatthe reaction of zinc with the addition are useful as solvents forfluorine-containing polymers, product, C BrCl F did not produce anolefin; reduction nsecticides, fire extinguishing agents, non-flammablehyoccurred instead to form a C HCI F Treatment of the draulic fluids,lubricating oil additives, and chemical interaddition product withsodium iodide in acetone did yield mediates. an olefin, but analysisshowed the olefin to be a C CI F The products of the present inventionmay also be proformed by the elimination of BrF instead-of a CRC1 Fduced using continuous flow techniques. expected by the elimination ofBrCl. The most highly The invention will be further illustrated byreference to fiuorinated product obtained on fiuorination of this olefinthefollowlng specific examples: was a C ClF This result indicated the'presencebf' a vinyl chlorine. Oxidation of the olefin yieldedtrifluoroacetic and trichloroacetic acids. The olefin wasassigned thestructure, CF CCl =CFCCl on the basis of the oxidation. e

To give rise to this olefin, the structure of the original additionproduct had to be cF,cBrc1cF,cc1,, instead of This orientation is inagreement with the prediction that attack by a CCl radical will takeplace on the most exposed position, the terminal CF group.

Z-bramo-Z,4,4,4-tetrachloropentafluorobulanel Commercial CBrCl wasdistilled before use, and the fraction boiling from 102 to 104 C. at 730mm. was utilized. In a typical run, 425 grams (2.14 moles) of CBrCl and295 grams 1.77 moles) of CF CCl=CF were placed in three Pyrex ampoules.The ampoules were wrapped with nichrome heating wire, placed in theS-bulb illuminator, and heated so that thermocouples taped to theoutside of the ampoules read 120-130 C. The heating and illumination wascontinued for seven days. The combined contens of the ampoules weredistilled to yield:

The portion of Fraction 3, 210 grams, was redistilled to yield thefollowing fractions:

(5) B.P. 80 C./100 to 119.2 -o./1 o0,mm.,-11 grams 3 C./100 mm., 277grams.

' (6) B.P. 119.2 to 119.5 C./100 mm., 24 grams, RP.

(7) B.P. 119.5 to 119.7" C./100 mm., 28 grams, F.P.

-59.2 to 60.5 C. l (8) B.P. 119.7 C./100 mm., 90 grams, F.P. -58.5 C.(9) B.P. 119.7 C./100 mm., 30 grams, F.P. --58.5'to

58.7 C. 10. B.P. 119.7 to 119.9 C./100 mm., 18 grams, F. P.

-58.6 to 58.7 C. (11) Residue, 10 grams I The presence of largely oneisomer was indicated by the fact that 80 percent of the above materialfroze within one degree and 65 percent froze within one-tenth degree.

The properties were: B.P. 119.7 C./100 mm.; d3, 2.0374; n 1.4443; R1.-58.5 C. MR found, 47.58; calculated, 48.0.

Redistillation of the combined'foreruns from the recovered CBrClfractions through a Podbielniak column yielded about 0.2 weight percentof a fraction containing CHC13, and about'0.5 weight percent of afraction consisting mostly of CCl Several redistillations of thecombined residuesfrom the recovered CBrCl fractions yielded about one'weight percent of CF CBrClCBrF Identification of these materials was bymeans .of boiling point and infrared spectra. I

The combined residues fromv several reactions (Fraction 11 and fractionsobtained similarly, 330 grams) were redistilled to yield 100 grams of afraction boil,- ing at 100 C. at 3 mm. The properties. of this fractionwere: B.P. 100 C./3 mm.; d 1.9295; n 1.47.79; molecular weight 403, 406.

Although this compound was not positively identified, a likelypossibility is CF CCl(CCl )CF CCl, molecular weight 406. MR found,59.54; calculated, 59.60.

EXAMPLE 3 i Reduction of C.,BrCl F by zinc The addition product of aCBrCl and CF CCl=CF 63 grams, was added to a refluxing suspension ofzinc in dioxane. The resulting mixture was washed with dilute acid, thenwashed with water, dried, and distilled to yield:

( 1) B.P. 94=to 127 C., 7 grams (2) B.P. 127 to 79 C./100 mm., 3 grams(3) B.P. 79 to 80 C./100 mm., 10 grams (4) Residue, 22 grams Theproperties of Fraction 3 were: B.P., 140-143 C./ 738 mm.; d 1.7201; n1.4060.

In a similar reaction, 135 grams of the addition product were reactedwith zinc in dry ether and worked up as before. Distillation yielded:

, Grams (5) B.P. 34 C./100 mm. to 78 .C/lOO mm 26 (6) B.P. 78 to 81C./100 mm. 20 (7) Tarry black residue 15 8 B.P.166 to 173 C., 4.5 gramsp 9 B.P. 108" cms mm.,to132 c./11s mm., 4.5 grams (l0) B.P. 132 to 140C./1l5 mm., 5.0 grams Fraction 8 was redistilled to yield about'2 gramswith the following properties: B.P. 168.0 to 168.5 C./732 mm.; M.W. 316;Cl, 55.3 percent; F, 29.2, 29.8 percent.

Calculated for C CI F M.W., 320.3; Cl, 55.4 percent; F, 29.6 percent.

The apparent molecular weight of Fraction 10 was 338. Calculated forC.,Cl F 337. 1

-Reaction with sodium iodide in acetone.-In a smallscale reaction, itwas found that the addition product gave an immediate precipitate andiodine color with NaI in acetone. This reaction was then extended to alarge scale in order to 'study the product. p

The C BrCl F (253 grams, 0.695 mole) was added to a solution of 300grams (2 moles) of 'NaI in 1200 grams of QR acetone. The reactionmixture was shaken well and allowed to stand twenty-four hours at roomtemperature.

Themixture was then drowned in water and enough 30 percent sodiumhyposulfite solution added to remove the free iodine. After standing fortwenty-four hours, the organic layer was separated, dried, and distilledto yield:

(l) B.P. 27 to C., 5 grams (2) 130 to C., grams.

cent 7 (3) Residue; 12.5 grams (4) B.P. 42 to 130 C., 4 grams (5) B.P.130 to 138 C., 105 grams.

cent. e

( 6) Residue, 27 grams.

CRCl4F per "7 Fraction 5 was redistilled to yield the followingfractions:

(7) B.P. 133 to 136.0 C./737 mm., 8.3 grams (8) B.P. 136.0 to 136.3C./737 mm., 16.0 grams (9) B.P. 136.3 to 136.4 C./73S mm., 11.4 grams(10) B.P. 136.4 to 136.6 C., 10.5 grams (11) B.P. 136.6 to 136.8 C.,11.5 grams 12) B.P. 136.8 to 138 C./738 mm., 35 grams Fraction m. d4F.P., 0.

Fraction 12 had a reflux boiling point of l35 C. at 740 mm., and wasassumed to be mostly recovered C CI F Fraction 11, dd" F.P., C

MR for C Cl F found, 49.66; calculated: 50.04.

Oxidation of C Cl F .The olefin resulting from the sodium iodidereaction was oxidized using KMnO and NaHCO .A 30 percent excess of KMnOand a 100 percent excess of NaHCO was used. The solvent was 3:1 ratio byvolume mixture of water and C.P. acetone. About one liter of solvent permole of olefin was used. The oxidizing solution was cooled in iceand-the olefin (73 grams) was added slowly. After all the olefin hadbeen added, the mixture was warmed up to room temperature and stirredovernight.

The excess permanganate was removed bypassing in S The solution wasfiltered, acidified with H 80 and extracted for 48 hours with ether.

The ether layer was distilled to yield:

(1) B.P. 34 to 37 C., ether (2) B.P. 37 to 101 C., grams (3) B.P. 101 to102 C./740 mm., 13 grams.

, CF CO H-2H O, 30 percent p (4) B.P. 37 C./50 mm. to 125 C./50 mm., 2grams (5) B.P. 125 to 127 C./50 mm., grams. CCl C0 H,

23 percent (6) Residue, 1 gram The properties of Fraction 3, anazeotrope of CF CO H and water, containing 80 percent acid,were: d1.2343; 11 1.3156. The neutralization equivalent calculated for CF COH-2H O (80 percent acid) is 150; found, 147, 148. On refluxing withexcess ethanol, 5 grams of ester boiling at 59 to 60 C. at 741 mm. ,wascollected. The reported boiling point of ethyltrifluoroacetate is, 61.7C.

ethyl trichloroacetate, boiling at 165 C. at 740mm,

r 8 11, 1.4070. The reported boiling point of ethyl trichloroacetate is167 to 168 C.

A second oxidation of the olefin, 30 grams (0.11 mole), was run using asolid carbon dioxide reflux condenser. The oxidation was run and workedup as described above. Distillation yielded:

(7) B.P. 34 to 37 C., ether (8) B.P. 37 to 103 C., 2 grams. Intermediate(9) B.P. 103 to 105 C./744 mm., 11.6 grams.

CF CO H-2H O, 66 percent (10) B.P. 105 C./744 mm. to 119 C./50 mm., 1gram.

Intermediate (11) B.P. 119 to 122 C./50 mm.,

CCl CO H, 55 percent Fluorination of C CI F .'A steel bomb was filledwith 157 grams (0.59 mole) of C.,CI F from the sodium iodide reaction,250 grams (1.15 moles) of HgO, and 74 grams (3.7 moles) of HF and shakenfor twelve hours at 40 to 100 C. The contents were steam distilled fromthe bomb, steam distilled again, and the organic layer dried anddistilled to yield.

(1) Solid carbon dioxide trap, 1.6 grams (2) B.P. 30 to 60 C., 3 grams(3) B.P. 60 to 67 C., 54 grams.

(4) B.P. 67 to C., 8.7 grams (5) B.P. 130 to 137 C., 7.5 C CI F 5percent (6) Residue, 4 grams Fraction 3 was redistilled through column Dto yield:

(7) B.P. 60 to 63.7 C., 15 grams (8) B.P. 63.7 to 63.8 C./730 mm., 9grams (9) B.P. 63.8 C./729 mm., 5 grams (10) Residue, 25 grams Theproperties of Fraction 9 were: d 1.5873; n 1.3381; F.P. 125.7 to 126.7C. MR for C.,CI F found, 30.6; calculated, 30.65.

Fractions 7, 8, and 10 (0.20 mole) were placed in a steel bomb with 55grams of HgO and 29 grams of HP. The bomb was placed in a rocker-shakerand heated at 60 C. for twelve hours and 125 C. for twenty hours. Thecontents were steam distilled out of the bomb, steam distilled again,dried, and distilled to yield:

(11) Solid carbon dioxide trap, 2 grams (l2) B.P. 30 to 35 C., 10 grams.C.,CIF 23 percent (13) B.P. 35 to 60 C., 3.5 grams (14) B.P. 60 to 65C., 23 grams.

I 7 49 percent (15) Residue, 1.5 grams Fraction 14 added chlorine toyield:

(16) B.P. 12s to 131,5" 0., 3 grams 17 B.P. 131.9 0774:) mm., 20.5 grams(18) Residue, 3 grams The properties of Fraction 17 were: d 1.7830; 111,3885; F.P. -89 to -91 C. MR for C C1 F found, 40.2; calculated, 40.7.Molecular weight calculated, 266; found 272. p

A third fluorination was run, using 84 grams (0.31 mole) of C CI F 170grams (0.78 mole) of HgO, and 50 grams (2.5 moles) of HF. The bomb wasrocked at room temperature for twelve hours; the temperature was thenraised to :5 C. over a twelve-hour period, and held there for twelvehours. The bomb was emptied and the contents worked up in the abovemanner. Distillation yielded:

10.5 grams.

C Cl F 39 percent grams. Recovered Recovered C 01 P Grams (19) Solidcarbon dioxide trap 5 (20) B.P. 30 to 32 C. 16 (21) B.P. 32 to 105 C 13(22) Residue 3 1 CRCIF I, 24 percent.

Fraction 20 was redistilled to yield 4.5 grams boiling at 31.0 to 31.5C. at 739 mm. The properties of this fraction were: B.P. 32.3 C./760mm.; d 1.5372; n 1.294. MR for C ClF- found, 2 5.8; calculated, 26.0.Molecular weight calculated for C ClF ,,216.4; found 216. The compoundcontained chlorine, was unsaturated to KMn but showed no reaction whenheated with sodium iodide in acetone at 100 C. for two hours. It addedchlorine to yield 4 grams boiling at 96.0 to 96.5 C. at 738 mm. with thefollowing physical properties: B.P., 97.5" C./760 mm.; d 1.7458; r11.3524. MR for C Cl F found, 35.6; calculated 36.0.

Reported properties for CF CCl=CFCF B.P., 32.2 0.; d3 1.5482; 11 1.2946;and CF CCl CClFCF B.P., 97.5 C.; d 1.7494; 11 1.3530.

The above C Cl F and a sample of CF CCl CClFCF isolated as the CIFaddition by-product inthe'reaction of F, with CF CCl=CClF were treatedwith zinc in dioxane. The infrared spectra of the products wereidentical.

Fraction 21 was redistilled into the following fractions:

' (23 B.P. 64 to 104.5 C., 3 grams 2 (24) B.P. 104.5 to 105.5 C./738mm., grams (25) Residue, 3 grams EXAMPLE 4 Preparation ofbromodichlorofluoromethane CHCl F, was passed through bromine, heated to32 to 36 C. by an oil bath, then through a 12 x 250 mm. Pyrex tubeheated at 475 5 C., using a calculated contact time of from two to fiveseconds. Excess bromine.

and HBr were removed by bubbling the vapors through a 20 percentNaOI-I-Na SO solution. The product was dried over CaCl Distillation of atypical run yielded:

(1) B.P. 8-9 to 49 C., 183 grams. Recovered CHClgF- (2) B.P. 49 to 50.2C., 35 grams (3) B.P. 50.2" C./734 mm., 31 grams (4) B.P. 50.2 C., 46grams (5) Residue, 8 grams The properties of Fraction 3, CBrCl F, were:B.P. 51.3 C./760 mm.; d 1.9317; n 1.4304; F.P., --106.4 C. MR found,24.34; calculated, 23.94.

EXAMPLE 5 The physical properties of the purest samples of novelcompounds characterized are summarized below:

FORMAT Molecular Formula-Compound Name-Structura.l

Formula Source:

B.P. (boiling point at the prevailing atmospheric pressure) B.P./760(boiling point corrected to one atmosphere) B.P. range RP. 2(equilibrium temperature of first appearance of crystals) F.P. dep.(depression from t, to the point at which, the

material was estimated to be half frozen) F.P. calc. (estimated fromcooling curve) 'MR (molecular refractivity calculated using the Lorentz-Lorenz equation) Source: Br +CF CCl=CF Propane,1,2-dibromo-2-chloropentafluoro- C BrCl F Butane,2-bromo-2,4,4,4-tetrachloropentafluo- B.P. 119.7,? ,C./100 mm. F.P. 58.5C. RP. dep. 0.1 C. d 2.0374 n 2-; a i 1.4443 MR Y 47.6

B.P./760 65.2 C. B.P. range 0.1 C. F.P. 1,1 -125.7% F.P..dep.. 0.5.c.F.P-. calc. 125.2 C. d gl/ml. 1.5873 n' I p 1.3381 MR 30.6

C Cl F Butene-2,1,1,3-trichloropentafluoro- B.P. B.P./760 106.4 C. B.P.range 1 1 C.

(1. g./ml'. 1.6362 n t T 1.3548 MR 33.1 C,,Cl F Butene-2,1,1,1,3-tetrachlorotetrafluoro- Source: C BrCl F +NaI B.P. 136.3 C./744mm. B.P./760 137.0 C. B.P. range 0.2 C.

C Cl F5 Butane, 1,2,3,3-tetrachlorohexafluoro- B.P 1 31.s c./74o mm.B.P./760 132.4 C. B.P. range 0.1 C. F.P. t, 89 c.

. Elk-dep. 1 C.

51 2. calc. 88 C. d, g./ml. 1.7830 n 1.3885 MR 40.3

C Cl F "Butane, '1,1,1,3,3-pentachloropentafluoro- CCI CF CCMCE Source;C I-ICl F +Cl, v B.P. 168.4 C./732 mm. B.P./760 169.2 C. B.P. range v0.5 C.

C Cl F Butane, 1,1,1,2,3,S-heXachIorotetrafluOIm CCIQCCIFCCI' CF Source:C Cl F +Cl B.P 116 CJSO mm. F.P. t 3'8 C. RP. dep. 2 C. d g./ml. 1.856611;, 1.4599 MR 49.7

C HCI F Butane, 2,4,4,4-tetrachloro-1,1,1,3,3-pentafiuoro-CF CHC1CF CCl,

Source: C BrC1 F -l-Zn B P 79.5 C./100 B.P./760 143 C. B.P. range 0.5 C.at 100 mm. (1 g./ml. 1.7201 n 1.4080 MR 40.8

CBrCl F Methane bromodichlorofluoro Source: CHCl F+Br B.P 50.2 C./734mm. B.P./760 51.3" C. B.P. range 0'.1 C. RP. t -'106. 4 C. F.P. dep. 0.1C. d g./ml. 1.9317 n 1.4304 MR 243 It will be obvioustothose' skilled inthe art that many modifications may be made within th'e'scope of thepresent invention without departing fromthe spirit -thereof,'-andtheinvention includes all such modifications.

I claim:

1. A process which comprises eifecting the-reaction under free radicalconditions initiated solely by photochemical dissociation of a compoundhaving the formulain which Y is selected from the group consisting offluorine and chlorine and R is selected from the group consisting ofperhaloalkyl an'd' perhaloalkenyl radicals having not more than about 8carbon atoms and in which all of the halogen atoms have atomic weightsnot in excess-of 35.46

to produce a monomeric addition product.

2. A process for thepreparation ofvthe compound" (3P (-BBi'I- CF 'CCL;

which comprises effecting the reaction under free radical conditionsinitiated solely by photochemical dissociation of the compound CBrClwith the compound CF CF"=CF 3. A process for. therpreparation. of'thelcompound CFQCBrCICFgCCl which comprises effecting the reaction'underfree radical conditions. initiated solely. by photochemicaldissociation of the. compoundCBrcl with thecompound- 12 4; Compoundshaving the formula in which X isselected from the group consisting offluorine and chlorine.

5. Compounds having the formula i o1-( )cF=oC1cF,

in which X and X are selected from the group consisting of fluorine andchlorine.

6; A'compound' having the formula 7. A compound having the formulaCClzFCF=CClCF3 8; A compound having the'formula CC1 CF=CClCF 9. Aprocess which comprises efiecting the reaction under free radicalconditions of a compound havingthe formula Xi i'n which'X is selectedfrom the group consisting of fluorine, chlorine and perhaloalkylradicals having not more than eight carbon atoms'and in which all of thehalogen atoms have atomic weights not in excess of 35.46; and X andXgare selected from the group consisting of chlorine and fluorine; with acompound having the formula in which Y is selected from the groupconsisting of fiuorine'and chlorine and R is selected from the groupconsisting of perhaloalkyl and perhaloalkenyl radicals having not morethan eight carbon atoms and in which all of the halogen atoms haveatomic weights not in excess'of 35.46; to produce a monomeric additionproduct; and reacting the monomeric addition product with sodium iodideto produce a perhalogenated alkene containing more carbon atoms than theinitial perhalogenated alkene.

10. A process for the preparation of the compound CCI CF=CCICF whichcomprises effecting the reaction under. free radical-conditions of thecompound CBrCl with the compound CF CCl=CF to produce the compound CFCBrClCF CCl3 and reacting CF CBrClCF CCl with sodium iodide to produce1,1,l,3-tetrachloro-2,4,4,4- ttraflirorobutene-Z;

11. A process for the preparation of the compounds CCI FCF=CCICF andCClF CF=CClCF which comprises efiecting the reaction under free radicalconditions of the compound'CBrCl with the compound CF CCl=CF to'produce"the compound 'CF CBrClCF CCl reacting CF CBrClCF CCl 'with sodium iodideto produce" CF CCl=CFCCl and reacting CF CCl=CFCCl with mercuricoxide-hydrogen fluoride. I

12. A process which comprises effecting the'reaction under freeradical-conditions of a compound'having' the orine, chlorine, andperhaloalkyl radicals having not more than eight carbon atoms and inwhich all of the halogen 13 atoms have atomic weights not in excess of35.46; and X and X, are selected from the group consisting of chlorineand fluorine; with a compound having the formula CF CYR in which Y isselected from the group consisting of fluorine and chlorine and R isselected from the group consisting of perhaloalkyl and perhaloalkenylradicals having not more than eight carbon atoms and in which all of thehalogen atoms have atomic weights not in excess of 35.46; to produce amonomeric addition product; reacting the monomeric addition product withsodium iodide to produce a perhalogenated alkene containing 14 morecarbon atoms than the initial perhalogcnated alkene and chlorinating theproduct thus obtained.

13. A process which comprises efiecting the reaction under free radicalconditions of the compound CBrCl with the compound CF CCl=CF to producethe compound CF CB1'ClCF CC1 reacting CF CBrClCF CCl with sodium iodideto produce CF CCI=CFCCI reacting CF CC1=CFCCl with mercuricoxide-hydrogen fluoride and chlorinating the product thus produced.

Gochenour et a1 Feb. 17, 1948 Dittman et al Apr. 5, 1955 UNITED STATESPATENT OFFICE Certificate of Correction Patent No. 2,880,248 March 31,1959 William T. Miller It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionand that the said Letters Patent should read as corrected below.

Columns 3 and 4:, approximately lines 33 and 34, should read 01 one 01,0aurora 4-- 0 F30 C1=CFC F3 column 5, lines 22 and 23, for contens read-contents-; column 8, line 58, for 1,3885 read -1.3885.

Signed and sealed this 18th day of August 1959.

[SEAL Attest: KARL H. AXLINE, ROBERT C. WATSON, Attesting Oyfiaer.Commissioner of Patents.

1. A PROCESS WHICH COMPRISES EFFECTING THE REACTION UNDER FREE RADICAL CONDITIONS INITIATED SOLELY BY PHOTOCHEMICAL DISSOCIATION OF A COMPOUND HAVING THE FORMULA 